Isoolefin-multiolefin copolymer oils



United States Patent 1 3,092,675 ISOOLEFIN-MULTIOLEFIN COPOLYMER OILS Apgustus B. Small, Westfield, NJ., assignor to Esso Research and Engineering Company, a corporation of quantities of hexane; the copolymer oils obtained being fractionated into two different oily copolymers by distillation under 100 mm. pressure absolute and at 200 C.

Delaware to produce 86.8 to 99.7 weight percent of heavy co- N0 Drawing. Filed May 25, 1959, Ser. No. 815,802 Polymer oi t balance g a light copolymer oilf -3 Claims. (Cl. 260--683.15) The reaction conditions and products formed were as This invention relates to the production of new and follows! Feed Catalyst Light Poly Heavy lnspecggfi 13g rHeavy Reactor mer Oil, Polymer Average Wt. Per- Oil, Wt. Isobutylls re H x ne, A1013, Temp., 0. cent Percent Viscosity, Mole Perene, wt. w P grams poise at 75 cent Unsat- Percent cent F. uration 91 9 1, 000 7 56 13. 2 86. 8 0. 5 21. 3 80 2o 1, 000 7 54 1. 4 98.6 3. 2 15. 4 so 20 1, 000 21 6. 3 93. 7 75. 0 10. 9 8o 4, 000 80 47 1. 7 98. 3 10.7 15. 2 75 4, 000 80 55 2.1 97. 9 9. 8 16. a 75 25 4, 000 80 60 3.4 98. 6 7. 5 17. 6 75 25 4, 000 80 44 o. 8 9o. 7 34. o 13.8 60 4o 1, 000 10 55 1.3 98.7 220. 0 15. 3

useful gel-free isoolefin-multiolefin copolyrner oils having The above (13121 Show that isobutylehe'isopl'ehe P Y' mole percent unsaturations of about 3 to 50 and viscosities H161 Oils are Produced in ahcol'dahce with Present of about 0.1 to 1,000 poises. There has been consider- 25 invention having t0 220-0 P0ises Viscosity at 75 F. able interest in the fields of synthetic high unsaturation and t0 mole Percent llllsatlll'atiohsrubbers such as GR-S rubber butadiene-styrene rubber) Resort y be had to modifications and Variations of for the production of such synthetic oils useful as rubber the disclosed embodiments Without departing from Th6 plasticizers. Also, in the field of lubricating oils, such SPiIit'Of the invention or the Scope of the pp Claimssynthetic oils have been desired as intermediates in the What is Claimed production of lubricating 511 additives. 1. A pr for Producing a e y -i Heretofore, it has been considered to be impossible to Prene coPOIYIIWIT Oil which COHIPTiSES copolymefizihg produce such copolymer il i h ifici fl hi about 5 to 95 wt. percent each of isobutylene and isosaturation but without the simultaneous production of un- P in about 10 to 50Qv01umes P h of P- desirable geL comonomers of an admixture of a ma or proportion of I accordance i h h present invention, 1 f an inert reactlon diluent and, as a polymerization catalyst, polymer oils are produced at about 5 C. to about 150 C., to 30 PF Sald diluent of 'h f bl at about 10 to 100 C. by copolymerizing complexed aluminum chloride, at a copolymerization for about 1 to 100, preferably for about 2 to about 60 temperature of allout about for about 1 minutes, about 5 to 95 weight percent, advantageously 40 to about about 8 to 92 Weight percent, and preferably about 10 A P f= f 1 Whmh the to 90 i h percent h f a 3 to C8 i l fi Such as polymerization 18 carr ed out 1n about 20 to 100 volu1nes Z-methyI-I-butene, 3-ethyl-1-butene or especially isobu- Per Teactmg comonomel's of admlxtflre of tylene and a C; to C multiolefin such as myrcene, dian Inert 'dlluent Selected from P class cohslstlhg of methanyl, 11 or f bl a c to C6 or C8 saturated hydrocarbons and chlorinated dertvatives thereconjugated diolefin such as butadiene, dimethy-l butadiene, h abmlt to 30 Welght Percfiht of ahlmlhum piperylene or especially isoprene. The copolymerization wonder is desirably conducted to 100 percent conversion and in A Process P P e a f copolymel' the presence of about 10 to 500, advantageously about lsobutylene lsoPrene whlch compnses coholymel'lzlhg 15 to 150 and preferably about 20 to 100 volumes, per about 9 to 95 welght P f lsohutylehe with about 40 volume of reacting comonomers f an admixture f to 5 weight percent soprene in about 20 to 100 volumes about 0.05 or 0.1 to 20 or 30, preferably about 0.5 or Per P P P Teactmg cqmonomers of an ihert dlluent 1.0 to 4 or 5 weight percent of an uncomplexed aluminum contammg dlspersed abollt 1 to 5 welght P bromide or especially an uncomplexed aluminum chloride of uncomplexed alummum chlonde on 531d dlhlent catalyst 11 BCIS and Ticl4 being inoperative) at a temperature of about 20 to 70 C. for about 2 to persed in an inert diluent such as a C to C inert hydrommutescarbon or halogenated derivatives of such hydrocarbons, examples of which are hexane, heptane, naphtha, mineral References Cited m the file of this patent spirits, chloroform, trichloroethane, carbon tetrachloride, UNITED STATES PATENTS etc. The resulting cop olymer oils produced have vis- 60 2,431,461 calfee et a1. 25 1947 coslties 1n polses at 75 F. to about 0.1 to 1,000, ad- 2,553,651 Gessler May 22 1951 vantageously about 0.3 to 500 and preferably about 0.5 2,569,383 Leyonmark et a1 Sept 25 1951 1 3 05 the mole percent unsaturation of such oils being 2,582,411 Bloch et aL Ian 15 1952 about 5 to 50, advantageously about 5 to 35 and prefer- 2,657,246 Schneider et aL Oct 27, 1953 ab1y bout 10 to 25. It 15, of course, also poss ble to 2,773,051 Leary 4 1956 fractronate such copolymer 011s mto 2 or more 0118, de- 2,780,664 Semiuk 5 1957 Pendmg 111n the deslred 2,813,136 Mertz Nov. 12, 1957 I11 q i fl t g z the 2,818,460 Geiser Dec, 31, 19 7 presen inven 1011, e o owing experimen a a a are given wherein 1 volume of various ratios of isobutylene OTHER REFERENCES and isoprene were copolymerized in the presence of 40 volumes of various amounts of A1Cl dispersed in various Thomas et al.: Jour. of Amer. Chem. Soc., 1932, vol. 54, pages 2480-2484. 

1. A PROCESS FOR PRODUCING A GEL-FREE ISOBUTYLENE-ISOPRENE COPOLYMER OIL WHICH COMPRISES COPOLYMERIZING ABOUT 5 TO 95 WT. PERCENT EACH OF ISOBUTYLENE AND ISOPRENE IN ABOUT 10 TO 500 VOLUMES PER VOLUME OF REACTING COMONOMERS OF AN ADMIXTURE OF A MAJOR PROPORTION OF AN INERT REACTION DILUENT AND, AS A POLYMERIZATION CATALYST, 0.05 TO 30 WT. PERCENT BASED ON SAID DILUENT OF AN UNCOMPLEXED ALUMINUM CHLORIDE, AT A COPOLYMERIZATION TEMPERATURE OF ABOUT 5*C. TO ABOUT 150*C. FOR ABOUT 1 TO ABOUT 100 MINUTES. 